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CN102822302B - Acrylic pressure-sensitive adhesive compositions and acrylic adhesive tape - Google Patents

Acrylic pressure-sensitive adhesive compositions and acrylic adhesive tape Download PDF

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Publication number
CN102822302B
CN102822302B CN201180015964.8A CN201180015964A CN102822302B CN 102822302 B CN102822302 B CN 102822302B CN 201180015964 A CN201180015964 A CN 201180015964A CN 102822302 B CN102822302 B CN 102822302B
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methyl
acrylic
acrylic polymers
monomer
acrylate
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CN102822302A (en
Inventor
冈本昌之
丹羽理仁
秋山淳
重富清惠
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

A kind of acrylic pressure-sensitive adhesive compositions, is characterized in that, containing acrylic polymers (A), described acrylic polymers (A) containing having the vinyl monomer of nitrogen-atoms as monomeric unit in skeleton, and does not contain carboxyl group-containing monomer in fact; (methyl) acrylic polymers (B), the weight-average molecular weight of described (methyl) acrylic polymers (B) is more than 1000 and lower than 30000.This acrylic polymers (A) be by described vinyl monomer and following general formula (1) [in formula (1), R 1for hydrogen atom or methyl, R 2for the alkyl of alicyclic hydrocarbon radical or carbonatoms 1 ~ 12.] (methyl) acrylate of representing carries out copolymerization as neccessary composition and the multipolymer obtained.CH 2＝C(R 1)COOR 2（1）。

Description

Acrylic pressure-sensitive adhesive compositions and acrylic adhesive tape
Technical field
The present invention relates to acrylic pressure-sensitive adhesive compositions and acrylic adhesive tape.
Background technology
In the past, there is the acrylic adhesive tape of acrylic adhesive layer, there are excellent photostabilization, weathering resistance, oil-proofness etc., and there is the tackiness of excellent such as bounding force, resistance to rebound resilience and preserving property (cohesive force) etc. and the ageing resistance of such as thermotolerance, weathering resistance etc., be therefore widely used.Especially, there is the acrylic adhesive tape of such characteristic, widely use as the grafting material in the various industrial fields such as electrical article of being in, building materials, automotive interior trim and extraneous adornment.Therefore, require that acrylic adhesive tape is gluing with high reliability to various adherends (coalesced object thing) such as the metallic substance such as stainless steel or aluminium, polyethylene, polypropylene, polystyrene, ABS, various plastic material such as (methyl) acrylic resin, polycarbonate resin etc. or glass materials.
As raising acrylic adhesive tape to the method for the tackiness of adherend, in the known acrylic pressure-sensitive adhesive compositions forming acrylic adhesive layer, add the method for tackifying resin (tackifier).In patent documentation 1 and patent documentation 2, disclose the acrylic pressure-sensitive adhesive compositions of rosin or the hydrogenated petroleum resin be added with in acrylic polymers as tackifying resin.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-207151 publication
Patent documentation 2: Japanese Kohyo 11-504054 publication
Summary of the invention
Always require to improve acrylic adhesive tape to the tackiness of adherend, be particularly strongly required to improve in electrical article of being in, building materials, automotive interior trim, external decorative material etc. a large amount of that use, with the tackiness of the polyolefin resin such as polyethylene, the polypropylene low polarity adherend that is representative.On the other hand, be added with the aforesaid propylene acrylic binder composition of the tackifying resins such as rosin, sometimes fully can not tackle and wish that acrylic adhesive tape improves the requirement to the tackiness of low polarity adherend.
The present invention foundes in view of such problem, its object is to the technology providing the tackiness that can improve acrylic adhesive tape.
A certain mode of the present invention is acrylic pressure-sensitive adhesive compositions.This acrylic pressure-sensitive adhesive compositions, is characterized in that, containing acrylic polymers (A), described acrylic polymers (A) containing having the vinyl monomer of nitrogen-atoms as monomeric unit in skeleton, and does not contain carboxyl group-containing monomer in fact; (methyl) acrylic polymers (B), the weight-average molecular weight of described (methyl) acrylic polymers (B) is more than 1000 and lower than 30000.
By the acrylic pressure-sensitive adhesive compositions of which, the tackiness of acrylic adhesive tape can be improved.
In the acrylic pressure-sensitive adhesive compositions of aforesaid way, the multipolymer that acrylic polymers (A) can carry out copolymerization for (methyl) acrylate vinyl monomer and following general formula (1) represented as neccessary composition and obtain,
CH 2＝C(R 1)COOR 2（1）
In formula (1), R 1for hydrogen atom or methyl, R 2for the alkyl of alicyclic hydrocarbon radical or carbonatoms 1 ~ 12.
In addition, in the acrylic pressure-sensitive adhesive compositions of aforesaid way, vinyl monomer can for being selected from one or more monomers in group that the N-vinyl cyclic acid amides that represented by following general formula (2) and (methyl) acrylic amide form,
In formula (2), R 3for the organic group of divalence.
In addition, in the acrylic pressure-sensitive adhesive compositions of aforesaid way, the content of (methyl) acrylic polymers (B) can be 2 ~ 70 weight parts relative to acrylic polymers (A) 100 weight part.
Another way of the present invention is acrylic adhesive tape.This acrylic adhesive tape, is characterized in that, has the binder layer of the acrylic pressure-sensitive adhesive compositions containing above-mentioned either type.
Invention effect
According to the present invention, the tackiness of acrylic adhesive tape can be improved.
Embodiment
The acrylic pressure-sensitive adhesive compositions of present embodiment, containing the acrylic polymers (A) as adhesive composition and the weight-average molecular weight more than 1000 as tackifying resin and lower than 30000 (methyl) acrylic polymers (B) (following, to be suitably called (methyl) acrylic polymers (B)).Below, acrylic polymers (A) and (methyl) acrylic polymers (B) are described in detail.
[acrylic polymers (A)]
Acrylic polymers (A) has the vinyl monomer of nitrogen-atoms as monomeric unit for containing in skeleton, and the polymkeric substance in fact not containing carboxyl group-containing monomer.In the acrylic pressure-sensitive adhesive compositions of present embodiment, by making in acrylic polymers (A) containing the vinyl monomer in skeleton with nitrogen-atoms, as monomeric unit, acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) can be made to have the polarity of appropriateness.And, by making not contain carboxyl group-containing monomer in fact in acrylic polymers (A), can prevent the polarity of acrylic polymers (A) from excessively improving.Thus, the tackiness of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) to low polarity adherend can be improved.In addition, owing to not containing carboxyl group-containing monomer in fact in acrylic polymers (A), therefore can improve and there is the affinity of low polarity to (methyl) acrylic polymers (B) of moderate polarity.Thus, the bounding force of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape), resistance to rebound resilience and preserving property can be improved simultaneously.In addition, though by acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) for optical applications when, also can improve the transparency of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape).In addition, owing to not containing carboxyl group-containing monomer in fact in acrylic polymers (A), therefore can prevent from corroding adherend.
At this, described " carboxyl group-containing monomer ", refers in a molecule vinyl monomer (ethylenically unsaturated monomer) with at least one carboxyl (can be the form of acid anhydrides).As the concrete example of described carboxyl group-containing monomer, can enumerate: olefinic unsaturated monocarboxylic acid, as (methyl) vinylformic acid, β-crotonic acid etc.; Olefinic unsaturated dicarboxylic acid, as toxilic acid, methylene-succinic acid, citraconic acid etc.; The acid anhydrides of olefinic unsaturated dicarboxylic acid, as maleic anhydride, itaconic anhydride etc.; Deng.In addition, described " not containing in fact " refers to that such as acrylic polymers (A) is not completely containing carboxyl group-containing monomer, or its content is less than 0.1 % by weight of whole monomer component.In addition, described " in fact not containing " refers to that carboxyl contained in such as acrylic polymers (A) is below 0.0014mol/g equivalent.
Acrylic polymers (A) is not preferably not only in fact containing carboxyl group-containing monomer, and the monomer in fact not containing the acidic-group had beyond carboxyl (sulfonic group, phosphate etc.).That is, be preferably less than 0.1 % by weight of whole monomer component completely containing carboxyl group-containing monomer with containing other acidic-group monomer or its total amount.Or carboxyl contained in acrylic polymers (A) and the total amount of other acidic-group are preferably below 0.0014mol/g equivalent.
In addition, acrylic polymers (A), the multipolymer that such as, (methyl) acrylate for the vinyl monomer and following general formula (1) in skeleton with nitrogen-atoms being represented carries out copolymerization as neccessary composition and obtains,
CH 2＝C(R 1)COOR 2（1）
In formula (1), R 1for hydrogen atom or methyl, R 2for the alkyl of alicyclic hydrocarbon radical or carbonatoms 1 ~ 12.
Acrylic polymers (A) can obtain by vinyl monomer and (methyl) acrylate being carried out being polymerized (such as, solution polymerization, letex polymerization, UV polymerization) under the existence of polymerization starter.At this, described " as neccessary composition copolymerization " refers to, the total amount of described vinyl monomer and described (methyl) acrylate is more than about 50 % by weight of the monomer component total amount forming acrylic polymers (A).The total amount of described vinyl monomer and described (methyl) acrylate is more than about 50 % by weight relative to monomer component total amount and less than 99.9 % by weight, preferably more than about 60 % by weight and less than 95 % by weight, more preferably from about more than 70 % by weight and less than 85 % by weight.
There is the vinyl monomer of nitrogen-atoms in skeleton, be preferably selected from one or more monomers in the group that the N-vinyl cyclic acid amides that represented by following general formula (2) and (methyl) acrylic amide form,
In formula (2), R 3for the organic group of divalence.
As the concrete example of N-vinyl cyclic acid amides, can enumerate: NVP, N-vinyl-2-piperidone, N-vinyl-3-morpholone mai, N-vinyl-2-hexanolactam, N-vinyl-1,3- piperazine-2-ketone, N-vinyl-3,5-morpholine diketone etc.
As the concrete example of (methyl) acrylic amide, can enumerate:
(methyl) acrylamide;
N-alkyl (methyl) acrylamide, as N-ethyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide etc.; With
N, N-dialkyl group (methyl) acrylamide, as N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-di-n-butyl (methyl) acrylamide, N, N-di-t-butyl (methyl) acrylamide etc.; N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide etc.In addition, these vinyl monomers may be used singly or two or more in combination.
As other than the above, that there is nitrogen-atoms in skeleton vinyl monomer, can enumerate:
Succinimide class monomer, as N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxygen base hexa-methylene succinimide, N-(methyl) acryl-8-oxygen base eight methylene radical succinimide etc.;
Maleimide monomer, as N-N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenylmaleimide etc.;
Clothing health acid imide monomer, as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide etc.;
Nitrogen-containing hetero lopps monomer, as N-methyl ethylene pyrrolidone, N-vinylpyrazine, N-vinyl imidazole, N-vinyl azoles, N-(methyl) Antiepilepsirin, N-(methyl) acryloyl tetramethyleneimine, N-polyvinyl morpholinone, N-vinyl pyrrole, N-vinyl be different azoles, N-vinylthiazole, N-vinyl isothiazole, N-vinyl pyridazine, N-(methyl) acryl-2-Pyrrolidone, N-vinyl pyridine, N-vinyl pyrimidine, N-vinyl piperazine, N-vinyl pyrrole etc.;
Lactams monomer, as N-caprolactam etc.;
(methyl) acrylate class monomer, as (methyl) acrylate, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) tbutylaminoethylacrylate etc.;
Containing isocyanate group monomer, as (methyl) vinylformic acid-2-isocyanato ethyl etc.;
Acryloyl morpholine;
N-vinylcarboxamide class; Deng.These vinyl monomers may be used singly or two or more in combination.
As vinyl monomer, the N-vinyl cyclic acid amides that can be more suitable for using above-mentioned general formula (2) to represent and (methyl) acrylic amide.In addition, the R in above-mentioned general formula (2) 3, be preferably saturated or undersaturated alkyl, more preferably saturated hydrocarbyl (such as, the alkylidene group of carbonatoms 3 ~ 5).As particularly preferred N-vinyl cyclic acid amides, NVP, N-vinyl-2-hexanolactam can be enumerated.In addition, as particularly preferred (methyl) acrylic amide, N can be enumerated, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide.
As the concrete example of (methyl) acrylate that above-mentioned general formula (1) represents, can enumerate:
(methyl) alkyl acrylate, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) ethyl acrylate (2-ethylhexyl (methyl) acrylate), (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) lauryl ester etc.,
There is (methyl) acrylate of alicyclic hydrocarbon radical, as (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.;
There is (methyl) acrylate of aryl, as (methyl) phenyl acrylate etc.;
(methyl) acrylate obtained by the alcohol derivate of terpenoid; Deng.These (methyl) acrylate may be used singly or two or more in combination.In addition, (methyl) vinylformic acid refers to acrylate and/or methacrylic ester, " (methyl) ... " the implication that whole expression is same.
In addition, in order to improve cohesive force, thermotolerance, bridging property etc., acrylic polymers (A) as required can containing can with other monomer component (copolymerisable monomer) of described vinyl monomer and (methyl) acrylic ester copolymer.Therefore, acrylic polymers (A) can simultaneously containing as the vinyl monomer of main component and (methyl) acrylate and copolymerisable monomer.
As the concrete example of copolymerisable monomer, can enumerate:
Vinyl ester, as vinyl-acetic ester, propionate etc.;
Cyano-containing monomer, as vinyl cyanide, methacrylonitrile etc.;
(methyl) alkoxyalkyl acrylate class monomer, as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate etc.;
Hydroxyl monomer, as (methyl) hydroxyalkyl acrylate etc. of such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, methacrylic acid hydroxyl lauryl, methacrylic acid (4-hydroxymethylcyclohexyl) methyl esters etc.;
Styrene monomer, as vinylbenzene, alpha-methyl styrene etc.;
Containing the acrylic monomer of epoxy group(ing), as (methyl) glycidyl acrylate etc.;
Glycols acrylate monomer, as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl polypropylene glycol ester etc.;
There is the acrylic ester monomer of heterocycle, halogen atom, Siliciumatom etc., as (methyl) tetrahydrofurfuryl acrylate, fluorine-containing (methyl) acrylate, polysiloxane (methyl) acrylate etc.;
Olefin monomer, as isoprene, divinyl, iso-butylene etc.;
Vinyl ethers monomer, as methylvinylether, ethyl vinyl ether etc.;
Aromatic ethenyl compound, as Vinyl toluene, vinylbenzene etc.;
Alkene or dienes, as ethene, divinyl, isoprene, iso-butylene etc.;
Vinyl ethers, as vinyl alkyl ethers etc.;
Vinylchlorid; Deng.These copolymerisable monomers may be used singly or two or more in combination.
As the usage quantity of copolymerisable monomer, be not particularly limited, usually can containing 0.1 ~ about 40 quality % that has an appointment, preferably about 0.5 ~ about 30 quality %, further preferred about 1 ~ about 20 quality % copolymerisable monomer relative to the monomer component total amount for the preparation of described acrylic polymers (A).
By containing the above copolymerisable monomer of 0.1 quality % of having an appointment, can prevent the cohesive force of the acrylic adhesive tape or adhesive sheet with the binder layer formed by acrylic pressure-sensitive adhesive compositions from declining, can high shear force be obtained.In addition, by the content of copolymerisable monomer is set as below about 40 quality %, can prevent cohesive force from excessively raising, the sticky feeling under normal temperature (25 DEG C) can be improved.
In addition, in order to regulate the cohesive force of formed acrylic pressure-sensitive adhesive compositions, in acrylic polymers (A), polyfunctional monomer can be contained as required.
As polyfunctional monomer, can enumerate such as: (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, 1, 2-ethylene glycol bisthioglycolate (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 1, 12-dodecanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, epoxy acrylate, polyester acrylate, urethane acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate etc.Wherein, trimethylolpropane tris (methyl) acrylate, hexylene glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate can suitably be used.Multifunctional (methyl) acrylate may be used singly or two or more in combination.
As the usage quantity of polyfunctional monomer, different according to its molecular weight or functional group number etc., relative to the monomer component total amount for the preparation of acrylic polymers (A), add about 0.01 ~ about 3.0 quality %, preferably about 0.02 ~ about 2.0 quality %, further preferred about 0.03 ~ about 1.0 quality %.
When the usage quantity of polyfunctional monomer exceedes about 3.0 quality % relative to the monomer component total amount for the preparation of acrylic polymers (A), such as, the cohesive force that sometimes there is acrylic pressure-sensitive adhesive compositions is too high, thus degradation situation under adhesive power.On the other hand, during lower than about 0.01 quality %, such as, sometimes there is degradation situation under the cohesive force of acrylic pressure-sensitive adhesive compositions.
< polymerization starter >
When preparing acrylic polymers (A), by utilizing the thermofixation reaction or ultraviolet curing reaction that use the polymerization starter such as thermal polymerization or Photoepolymerizationinitiater initiater (light trigger), acrylic polymers (A) easily can be formed.Particularly from considerations such as the advantages that can shorten polymerization time, suitably Photoepolymerizationinitiater initiater can be used.Polymerization starter may be used singly or two or more in combination.
As thermal polymerization, can enumerate such as: azo type polymerization initiator [such as, 2, 2 '-Diisopropyl azodicarboxylate, 2, 2 '-azo two-2-methylbutyronitrile, 2, 2 '-azo two (2 Methylpropionic acid) dimethyl ester, 4, 4 '-azo two-4-cyanopentanoic acid, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2, 2 '-azo two (2-amidine propane) dihydrochloride, 2, 2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, 2, 2 '-azo two (2-methyl-prop amidine) dithionate, 2, 2 '-azo two (N, N '-dimethyleneisobutylamidine) dihydrochloride etc.], peroxide type polymerization initiator [such as, dibenzoyl peroxide, the peroxidation toxilic acid tert-butyl ester, lauroyl peroxide etc.], redox Type of Collective initiator etc.
The usage quantity of thermal polymerization is not particularly limited, as long as the scope that can use as thermal polymerization in the past.
As Photoepolymerizationinitiater initiater; be not particularly limited, can use such as: benzoin ethers Photoepolymerizationinitiater initiater, acetophenones Photoepolymerizationinitiater initiater, α-one alcohols Photoepolymerizationinitiater initiater, aromatic sulfonyl class Photoepolymerizationinitiater initiater, photolytic activity oximes Photoepolymerizationinitiater initiater, bitter almond oil camphor class Photoepolymerizationinitiater initiater, dibenzoyl class Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, ketal class Photoepolymerizationinitiater initiater, thioxanthene ketone Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater etc.
Particularly, as benzoin ethers Photoepolymerizationinitiater initiater, can enumerate such as: benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-ketone [trade(brand)name: イ Le ガ キ ユ ア 651, Ciba Specialty Chemicals manufactures], phenylmethylether methyl ether etc.As acetophenones Photoepolymerizationinitiater initiater, can enumerate such as: 1-hydroxycyclohexylphenylketone [trade(brand)name: イ Le ガ キ ユ ア 184, Ciba Specialty Chemicals manufactures], 4-phenoxydichloroacetophenone, the 4-tertiary butyl-dichloroacetophenone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone [trade(brand)name: イ Le ガ キ ユ ア 2959, Ciba Specialty Chemicals manufactures], 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone [trade(brand)name: ダ ロ キ ユ ア 1173, Ciba Specialty Chemicals manufacture], methoxyacetophenone etc.As α-one alcohols Photoepolymerizationinitiater initiater, can enumerate such as: 2-methyl-2-hydroxypropiophenonepreparation, 1-[4-(2-hydroxyethyl) phenyl]-2-methylpropane-1-ketone etc.As aromatic sulfonyl class Photoepolymerizationinitiater initiater, can enumerate such as: 2-naphthalic sulfonic chloride etc.As photolytic activity oximes Photoepolymerizationinitiater initiater, can enumerate such as: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime etc.
In addition, in bitter almond oil camphor class Photoepolymerizationinitiater initiater, such as, bitter almond oil camphor etc. is comprised.In dibenzoyl class Photoepolymerizationinitiater initiater, such as, comprise dibenzoyl etc.In benzophenone Photoepolymerizationinitiater initiater, such as, comprise benzophenone, benzoylbenzoic acid, 3,3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone, Alpha-hydroxy cyclohexyl-phenyl ketone etc.In ketal class Photoepolymerizationinitiater initiater, such as, comprise dibenzoyl dimethyl ketal etc.In thioxanthene ketone Photoepolymerizationinitiater initiater, such as comprise thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone, dodecyl thioxanthone etc.
As acylphosphine oxide class Photoepolymerizationinitiater initiater, can enumerate such as: two (2,6-Dimethoxybenzoyl) phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl) (2,4,4-tri-methyl-amyl) phosphine oxide, two (2,6-Dimethoxybenzoyl) normal-butyl phosphine oxide, two (2,6-Dimethoxybenzoyl) (2-methylpropane-1-base) phosphine oxide, two (2,6-Dimethoxybenzoyl) (1-methylpropane-1-base) phosphine oxide, two (2,6-Dimethoxybenzoyl) tertiary butyl phosphine oxide, two (2,6-Dimethoxybenzoyl) cyclohexyl phosphine oxide, two (2,6-Dimethoxybenzoyl) octyl group phosphine oxide, two (2-anisoyl) (2-methylpropane-1-base) phosphine oxide, two (2-anisoyl) (1-methylpropane-1-base) phosphine oxide, two (2,6-diethoxy benzoyls) (2-methylpropane-1-base) phosphine oxide, two (2,6-diethoxy benzoyls) (1-methylpropane-1-base) phosphine oxide, two (2,6-dibutoxy benzoyls) (2-methylpropane-1-base) phosphine oxide, two (2,4-Dimethoxybenzoyl) (2-methylpropane-1-base) phosphine oxide, two (2,4,6-trimethylbenzoyls) (2,4-bis-pentyloxy phenyl) phosphine oxide, two (2,6-Dimethoxybenzoyl) benzyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2-phenyl propyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2-phenylethyl phosphine oxide, two (2,6-Dimethoxybenzoyl) benzyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2-phenyl propyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2-phenylethyl phosphine oxide, 2,6-Dimethoxybenzoyl benzyl butyl phosphine oxide, 2,6-Dimethoxybenzoyl octyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2,5-diisopropyl phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2-aminomethyl phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-4-aminomethyl phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2,5-diethyl phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2，3，5，6-tetramethylphenyl phosphine oxides, two (2,4,6-trimethylbenzoyl)-2,4-bis-n-butoxyphenyl phosphine oxide, TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl) isobutyl-phosphine oxide, 2,6-Dimethoxybenzoyl-2,4,6-trimethylbenzoyls-normal-butyl phosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2,4-dibutoxy phenyl phosphine oxide, 1,10-bis-[two (2,4,6-trimethylbenzoyl) phosphine oxide] decane, three (2-methyl benzoyl) phosphine oxide etc.
The usage quantity of Photoepolymerizationinitiater initiater, is not particularly limited, and such as, coordinates with the amount in the scope of about 0.01 ~ about 5 weight part, preferably about 0.05 ~ about 3 weight part relative to monomer component 100 weight part for the preparation of acrylic polymers (A).
At this, the usage quantity of Photoepolymerizationinitiater initiater be less than about 0.01 weight part time, polyreaction is insufficient sometimes.The usage quantity of Photoepolymerizationinitiater initiater exceed about 5 weight part time, sometimes cause ultraviolet can not reach binder layer inside because Photoepolymerizationinitiater initiater absorbs ultraviolet.Now percent polymerization declines, or the molecular weight of sometimes generated polymkeric substance diminishes.And therefore, the cohesive force of the binder layer formed declines, thus when being peeled off from film by binder layer, a part for binder layer to remain on film thus film can not recycle sometimes.In addition, Photoepolymerizationinitiater initiater may be used singly or two or more in combination.
In order to regulate cohesive force, linking agent can also be used except described polyfunctional monomer.Linking agent can use normally used linking agent, can enumerate such as: epoxies linking agent, isocyanates linking agent, polysiloxane-based linking agent, azoles quinoline class linking agent, aziridines linking agent, silane-type cross-linking agent, alkyl etherified melamine class linking agent, metallo-chelate class linking agent etc.Suitably can use isocyanates linking agent, epoxies linking agent especially.
Specifically, as the example of isocyanates linking agent, the affixture of tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenation of benzene dimethylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene multi-phenenyl isocyanate and the polyvalent alcohol such as they and TriMethylolPropane(TMP) can be enumerated.
As epoxies linking agent, dihydroxyphenyl propane, Epicholorohydrin type epoxy resin, ethylidene glycidyl ether, polyethylene glycol diglycidyl base ether, glycerine diglycidyl ether, glycerine triglycidyl group ether, 1 can be enumerated, 6-hexylene glycol glycidyl ether, trimethylolpropane tris glycidyl ether, diglycidylaniline, diamino glycidyl group amine, N, N, N ', on N '-four glycidyl group m-xylene diamine and 1,3-bis-(N-aminoglycidyl amino methyl) hexanaphthene etc.
In addition, consider to the adhering viewpoint of the optical components such as glass, the binder composition of present embodiment can suitably containing existing known silane coupling agent etc.
As described silane coupling agent, can enumerate such as: containing vinyl silicane coupling agent, as vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyltrimethoxy silane etc.; Containing styryl silane coupling agent, as to styryl Trimethoxy silane etc.; Containing (methyl) acryl silane coupling agents, as gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxyl silane, γ-acryloxypropyl Trimethoxy silane etc.; Containing epoxy silane coupling, as β-(3，4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxyl silane etc.; Containing amino silicane coupling agent, as N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl) gamma-amino hydroxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane etc.; The silane coupling agents such as γ-r-chloropropyl trimethoxyl silane, γ-mercaptopropyi methyl dimethoxysilane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, γ-isocyanatopropyl Trimethoxy silane.Silane coupling agent preferably containing epoxy group(ing), further preferred γ-glycidoxypropyltrime,hoxysilane.
The usage quantity of these silane coupling agents is generally 0.001 ~ 5 weight part relative to 100 parts by weight propylene acids polymers, the preferably ratio of 0.01 ~ 2 weight part.When the usage quantity of silane coupling agent is very few, the adhesivity to optical components such as glass can not be substantially improved, in addition, time too much, likely be difficult to adhesive property etc. to remain on good state.
In present embodiment, acrylic polymers (A) also can be prepared by the form of the partial polymer (acrylic polymers slurry) obtained coordinating the mixture irradiation ultraviolet radiation (UV) of described monomer component and polymerization starter to make monomer segment be polymerized.In acrylic polymers slurry, coordinate (methyl) described later acrylic polymers (B) to prepare acrylic pressure-sensitive adhesive compositions, be applied on predetermined applied thing by this binder composition, irradiation ultraviolet radiation can complete polymerization.In addition, the weight-average molecular weight (Mw) of acrylic polymers (A) is such as 30000 ~ 5000000.
[(methyl) acrylic polymers (B)]
(methyl) acrylic polymers (B) is less than the polymkeric substance of acrylic polymers (A) for weight-average molecular weight, works as tackifying resin, and has the advantage being difficult to cause inhibition when UV is polymerized.(methyl) acrylic polymers (B) such as contains (methyl) acrylate as monomeric unit.
As such (methyl) acrylate, can enumerate such as:
(methyl) alkyl acrylate, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Ethyl acrylate, (methyl) ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) lauryl ester etc.,
The ester of (methyl) vinylformic acid and alicyclic ring alcohol, as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.;
(methyl) aryl acrylate, as (methyl) phenyl acrylate, (methyl) benzyl acrylate etc.;
(methyl) acrylate obtained by the alcohol derivate of terpenoid; Deng.These (methyl) alkyl esters may be used singly or two or more in combination.
In addition, (methyl) acrylic polymers (B) can by by described (methyl) acrylate component unit and can with other monomer component (copolymerisable monomer) copolymerization of (methyl) acrylic ester copolymer and obtaining.
As can with other monomer of (methyl) acrylic ester copolymer, can enumerate:
Methacrylic alkyl esters monomer, as methoxyethyl methacrylate, ethoxyethyl methacrylates, methacrylic acid propoxy ethyl, methacrylic acid butoxyethyl, methacrylic acid oxyethyl group propyl ester etc.;
Salt, as methacrylic acid alkali metal salt etc.;
Two (methyl) acrylate monomer of (gathering) alkylene glycol, as two (methyl) acrylate, two (methyl) acrylate of Diethylene Glycol, two (methyl) acrylate of triethylene glycol, two (methyl) acrylate of polyoxyethylene glycol, two (methyl) acrylate of propylene glycol, two (methyl) acrylate of dipropylene glycol, two (methyl) acrylate etc. of tripropylene glycol of ethylene glycol;
Polynary (methyl) acrylate monomer, as trimethylolpropane tris (methyl) acrylate etc.;
Vinyl ester, as vinyl-acetic ester, propionate etc.;
Halogenated vinyl compounds, as vinylidene chloride; Methacrylic acid-2-chloroethene ester etc.;
Contain the polymerizable compound of azoles quinoline base, as 2-vinyl-2- azoles quinoline, 2-vinyl-5-methyl-2- azoles quinoline, 2-pseudoallyl-2- azoles quinoline etc.;
Polymerizable compound containing '-aziridino, as (methyl) acryloylaziridine, methacrylic acid-2-'-aziridino ethyl ester etc.;
Vinyl monomer containing epoxy group(ing), as allyl glycidyl ether, (methyl) glycidyl acrylate, (methyl) acrylic acid-2-ethyl glycidyl ester etc.;
Vinyl monomer containing hydroxyl, as the affixture etc. of the monoesters of (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid and polypropylene glycol or polyoxyethylene glycol, lactone and (methyl) 2-Hydroxy ethyl acrylate;
Fluorine-containing vinyl monomer, as (methyl) alkyl acrylate etc. that fluorine replaces;
Containing anhydride group monomer, as maleic anhydride, itaconic anhydride etc.;
Aromatic vinyl compound monomer, as vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.;
Vinyl monomer containing reactive halogen, as 2-chloroethyl vinyl ether, Monochloro Acetic Acid vinyl acetate etc.;
Vinyl monomer containing amide group, as (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-acryloyl morpholine etc.;
Succinimide class monomer, as N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxygen base hexa-methylene succinimide, N-(methyl) acryl-8-oxygen base eight methylene radical succinimide etc.;
Maleimide monomer, as N-N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenylmaleimide etc.;
Clothing health acid imide monomer, as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide etc.;
Nitrogen-containing hetero lopps monomer, as NVP, N-methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinylpiperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-vinyl azoles, N-(methyl) acryl-2-Pyrrolidone, N-(methyl) acryloylpiperidine, N-(methyl) acryl tetramethyleneimine, N-polyvinyl morpholinone, N-vinyl pyrazoles, N-vinyl be different azoles, N-vinylthiazole, N-vinyl isothiazole, N-vinyl pyridazine etc.;
N-vinylcarboxamide class;
Lactams monomer, as N-caprolactam etc.;
Cyano-containing monomer, as (methyl) vinyl cyanide etc.;
(methyl) acrylate class monomer, as (methyl) acrylate, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) tbutylaminoethylacrylate etc.;
Containing the monomer of imide, as N-cyclohexylmaleimide, isopropylmaleimide etc.;
Containing the monomer of isocyanate group, as (methyl) vinylformic acid-2-isocyanato ethyl etc.;
Containing organosilyl vinyl monomer, as vinyltrimethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, allyltrimethoxysilanis, trimethoxy-silylpropyl allylamine, 2-methoxy ethoxy Trimethoxy silane etc.
Hydroxyl monomer, as (methyl) acrylic acid hydroxy alkyl esters etc. such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, (methyl) dihydroxypropyl lauryl, methacrylic acid (4-hydroxymethylcyclohexyl) methyl esters;
There is the acrylic ester monomer of heterocycle, halogen atom, Siliciumatom etc., as (methyl) tetrahydrofurfuryl acrylate, fluorine-containing (methyl) acrylate, polysiloxane (methyl) acrylate etc.;
Olefin monomer, as isoprene, divinyl, iso-butylene etc.;
Vinyl ethers monomer, as methylvinylether, ethyl vinyl ether etc.;
Alkene or dienes, as ethene, divinyl, isoprene, iso-butylene etc.;
Vinyl ethers, as vinyl alkyl ethers etc.;
Vinylchlorid;
And there is at the monomer end obtained with vinyl polymerization the macromonomer class of the vinyl of free redical polymerization; Deng.These monomers can separately or combine and above-mentioned (methyl) acrylic ester copolymer.
In the acrylic pressure-sensitive adhesive compositions of present embodiment, as (methyl) acrylic polymers (B), can enumerate such as: the multipolymer of cyclohexyl methacrylate (CHMA) and Propenoic acid, 2-methyl, isobutyl ester (IBMA), the multipolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), the multipolymer of cyclohexyl methacrylate (CHMA) and acryloyl morpholine (ACMO), the multipolymer of cyclohexyl methacrylate (CHMA) and acrylamide (DEAA), the multipolymer of vinylformic acid-1-adamantane esters (ADA) and methyl methacrylate (MMA), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene base ester (DCPMA) and isobornyl methacrylate (IBXMA), methacrylic acid tetrahydrochysene dicyclopentadiene base ester (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), vinylformic acid tetrahydrochysene dicyclopentadiene base ester (DCPA), methacrylic acid-1-diamantane ester (ADMA), the homopolymer etc. that vinylformic acid-1-diamantane ester (ADA) is respective.
In addition, as (methyl) acrylic polymers (B), be preferably that the acrylic monomer with the structure of comparatively large vol of representative is as monomeric unit containing (methyl) acrylate there is such (methyl) aryl acrylate etc. of the ester of such (methyl) vinylformic acid of (methyl) acrylate of branched structure, (methyl) cyclohexyl acrylate or (methyl) isobornyl acrylate and alicyclic ring alcohol, (methyl) phenyl acrylate or (methyl) benzyl acrylate having ring texture using the alkyl that (methyl) tert-butyl acrylate is such.By the structure making (methyl) acrylic polymers (B) have such comparatively large vol, the tackiness of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) can be improved further.Consider from bulky viewpoint especially, the effect with the monomer of ring texture is high, and the effect of the monomer containing multiple ring is higher.In addition, when the synthesis of (methyl) acrylic polymers (B) or the making of binder composition time when adopting UV polymerization, from the viewpoint of being difficult to cause inhibition, preferably have the monomer of saturated bond, (methyl) acrylate that can be applicable to using alkyl to have branched structure or the ester that formed with alicyclic ring alcohol are as the monomer forming (methyl) acrylic polymers (B).
In addition, (methyl) acrylic polymers (B), can contain (methyl) acrylic monomer of the alicyclic structure such as with more than three rings as monomeric unit.By making (methyl) acrylic polymers (B) have the so bulky structure of the alicyclic structure of more than three rings, the tackiness of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) can be improved further.Especially, the tackiness for low polarity adherends such as polypropylene can be improved more significantly.(methyl) acrylic polymers (B) can have the homopolymer of (methyl) acrylic monomer of the alicyclic structure of more than three rings for this, or also can be (methyl) acrylic monomer of the alicyclic structure with more than three rings and the multipolymer of aforementioned (methyl) acrylate monomer or copolymerisable monomer.
(methyl) acrylic monomer, such as, (methyl) acrylate for being represented by following general formula (3).
CH 2＝C(R 4)COOR 5（3）
In formula (3), R 4for hydrogen atom or methyl, R 5for having the alicyclic hydrocarbon radical of the alicyclic structure of more than three rings.
Alicyclic hydrocarbon radical preferably has the three-dimensional arrangements such as caged scaffold.By making (methyl) acrylic polymers (B) containing alicyclic structures more than three rings with caged scaffold like this, the tackiness of acrylic pressure-sensitive adhesive compositions (acrylic adhesive tape) can be improved further.Especially, the bounding force to the low polarity adherend such as polyethylene, polypropylene can be significantly improved further.As the alicyclic hydrocarbon radical with caged scaffold, can enumerate such as: the tetrahydrochysene dicyclopentadiene base that following formula (3a) represents, the dihydro dicyclopentadiene base that following formula (3b) represents, the adamantyl that following formula (3c) represents, the tetrahydrochysene trimerization cyclopentadienyl that following formula (3d) represents, the dihydro trimerization cyclopentadienyl etc. that following formula (3e) represents.In addition, when the synthesis of (methyl) acrylic polymers (B) or the making of binder composition time when adopting UV polymerization, from the viewpoint of being difficult to cause inhibition, in (methyl) acrylic monomer containing alicyclic structures more than three rings with caged scaffold, be particularly suitable for use and there is the tetrahydrochysene dicyclopentadiene base that following formula (3a) represents, the adamantyl that following formula (3c) represents, (methyl) acrylic monomer of the saturated structures such as the tetrahydrochysene trimerization cyclopentadienyl that following formula (3d) represents is as the monomer forming (methyl) acrylic polymers (B).
In addition, as the example of (methyl) acrylic monomer of alicyclic structures more than such three rings containing having a caged scaffold, can enumerate: methacrylic acid tetrahydrochysene dicyclopentadiene base ester, vinylformic acid tetrahydrochysene dicyclopentadiene base ester, methacrylic acid tetrahydrochysene dicyclopentadiene 2-ethoxyethyl acetate, vinylformic acid tetrahydrochysene dicyclopentadiene 2-ethoxyethyl acetate, methacrylic acid tetrahydrochysene trimerization cyclopentadienyl ester, vinylformic acid tetrahydrochysene trimerization cyclopentadienyl ester, methacrylic acid-1-diamantane ester, vinylformic acid-1-diamantane ester, methacrylic acid-2-methyl-2-diamantane ester, vinylformic acid-2-methyl-2-diamantane ester, methacrylic acid-2-ethyl-2-diamantane ester, (methyl) acrylate such as acrylic acid-2-ethyl-2-diamantane ester.Should may be used singly or two or more in combination by (methyl) acrylic monomer.
In addition, can introduce in (methyl) acrylic polymers (B), with epoxy group(ing) or isocyanate group, there is reactive functional group.As the example of such functional group, can enumerate: hydroxyl, carboxyl, amino, amide group, sulfydryl.(copolymerization) is preferably used to have the monomer of such functional group when manufacturing (methyl) acrylic polymers (B).
The weight-average molecular weight of (methyl) acrylic polymers (B) is more than 1000 and lower than 30000, preferably more than 1500 and lower than 20000, further preferably more than 2000 and lower than 10000.When molecular weight is more than 30000, the bounding force that sometimes can not obtain self adhesive tape fully improves effect.In addition, lower than 1000 time, molecular weight is low, therefore sometimes causes the bounding force of self adhesive tape or confining force to decline.
The mensuration of weight-average molecular weight is by GPC method and carry out polystyrene conversion to obtain.Specifically, in the HPLC8020 that TOSOH Co., Ltd manufactures, use TSKGelGMH-H(20) × 2 as post, to measure under the condition of flow velocity 0.5ml/ minute at tetrahydrofuran solvent.
The content of (methyl) acrylic polymers (B), is preferably 2 ~ 70 weight parts relative to acrylic polymers (A) 100 weight part, further preferred 5 ~ 50 weight parts.During to add (methyl) acrylic polymers (B) more than 70 weight parts, the Young's modulus of the binder layer formed with the acrylic pressure-sensitive adhesive compositions of present embodiment is high, and the tackiness under low temperature is poor, even if or at room temperature also do not show bounding force.In addition, when addition is lower than 2 weight part, sometimes can not get its effect.
The second-order transition temperature (Tg) of (methyl) acrylic polymers (B) is more than about 20 DEG C and less than about 300 DEG C, preferably more than about 30 DEG C and less than about 300 DEG C, further preferably more than about 40 DEG C and less than about 300 DEG C.When second-order transition temperature (Tg) is lower than about 20 DEG C, the cohesive force of binder layer more than room temperature declines sometimes, and the tackiness under preserving property or high temperature declines.In present embodiment, the second-order transition temperature of the representative materials that can use as (methyl) acrylic polymers (B) is as shown in table 1.Second-order transition temperature shown in table 1 is the nominal value of record in document, products catalogue etc. or the value for calculating based on following formula (4) (Fox formula).
1/Tg=W1/Tg1+W2/Tg2+…+Wn/Tgn（4）
In formula (4), the second-order transition temperature (unit: K) of Tg represents (methyl) acrylic polymers (B), Tgi(i=1,2 ... n) represent the second-order transition temperature (unit: K) when monomer i forms homopolymer, Wi(i=1,2 ... n) weight fraction of monomer i in whole monomer component is represented.Above-mentioned formula (4) be (methyl) acrylic polymers (B) by monomer 1, monomer 2, the n kind monomer component of monomer n is formed time calculating formula.
Table 1
The composition of (methyl) acrylic polymers (B) Tg(℃) Remarks
DCPMA 175 The value that document etc. are recorded
DCPA 120 The value that document etc. are recorded
IBXMA 173 The value that document etc. are recorded
IBXA 97 The value that document etc. are recorded
CHMA 66 The value that document etc. are recorded
MMA 105 The value that document etc. are recorded
ADMA 250 The value that document etc. are recorded
ADA 153 The value that document etc. are recorded
DCPMA/IBXMA40 174 Calculated value (based on Fox formula)
DCPMA/MMA40 144 Calculated value (based on Fox formula)
DCPMA/MMA60 130 Calculated value (based on Fox formula)
IBXMA/MMA60 130 Calculated value (based on Fox formula)
ADMA/MMA40 180 Calculated value (based on Fox formula)
ADA/MMA40 132 Calculated value (based on Fox formula)
The compound that shortenings in table 1 is expressed as follows.
DCPMA: methacrylic acid tetrahydrochysene dicyclopentadiene base ester
DCPA: vinylformic acid tetrahydrochysene dicyclopentadiene base ester
IBXMA: isobornyl methacrylate
IBXA: isobornyl acrylate
CHMA: cyclohexyl methacrylate
MMA: methyl methacrylate
ADMA: methacrylic acid-1-diamantane ester
ADA: vinylformic acid-1-diamantane ester
The multipolymer of DCPMA/IBXMA40:60 weight part DCPMA and 40 weight part IBXMA
The multipolymer of DCPMA/MMA40:60 weight part DCPMA and 40 weight part MMA
The multipolymer of DCPMA/MMA60:40 weight part DCPMA and 60 weight part MMA
The multipolymer of IBXMA/MMA60:40 weight part IBXMA and 60 weight part MMA
The multipolymer of ADMA/MMA40:60 weight part ADMA and 40 weight part MMA
The multipolymer of ADA/MMA40:60 weight part ADA and 40 weight part MMA
<(methyl) the making method > of acrylic polymers (B)
(methyl) acrylic polymers (B) such as can utilize solution polymerization process, mass polymerization, emulsion polymerization, suspension polymerization, block polymerization etc. (methyl) acrylic monomer polymerization with said structure to be made.
<(methyl) the Methods of molecular weight regulation > of acrylic polymers (B)
In order to regulate the molecular weight of (methyl) acrylic polymers (B), can usage chain transfer agent in its polymerization.As used chain-transfer agent, the compound with sulfydryl can be enumerated, as octyl mercaptan, tertiary nonyl mercaptan, lauryl mercaptan, tertiary lauryl mercaptan, mercaptoethanol, α-thioglycerin etc.; Thiovanic acid, Methyl Thioglycolate, ethyl thioglycolate, Thiovanic acid propyl ester, Thiovanic acid butyl ester, the Thiovanic acid tert-butyl ester, thioglycollic acid-2-ethyl hexyl ester, Thiovanic acid monooctyl ester, isooctyl mercaptoacetate, Thiovanic acid ester in the last of the ten Heavenly stems, Thiovanic acid dodecane ester, the mercaptoacetate of ethylene glycol, the mercaptoacetate of neopentyl glycol, the mercaptoacetate of tetramethylolmethane.From the viewpoint of metal protection, as particularly preferred chain-transfer agent, can enumerate: α-thioglycerin, mercaptoethanol, Methyl Thioglycolate, ethyl thioglycolate, Thiovanic acid propyl ester, Thiovanic acid butyl ester, the Thiovanic acid tert-butyl ester, thioglycollic acid-2-ethyl hexyl ester, Thiovanic acid monooctyl ester, isooctyl mercaptoacetate.
As the usage quantity of chain-transfer agent, be not particularly limited, usually relative to (methyl) acrylic monomer 100 weight part, containing the chain-transfer agent of 0.1 ~ about 20 weight part of having an appointment, preferably about 0.2 ~ about 15 weight part, further preferred about 0.3 ~ about 10 weight part.By regulating the addition of chain-transfer agent like this, (methyl) acrylic polymers (B) that molecular weight is suitable can be obtained.In addition, chain-transfer agent may be used singly or two or more in combination.
The acrylic pressure-sensitive adhesive compositions of present embodiment, containing above-mentioned acrylic polymers (A) and (methyl) acrylic polymers (B) as neccessary composition, can containing various additives general in binder composition field as any composition.As described any composition, softening agent, tenderizer, weighting agent, tinting material (pigment, dyestuff etc.), antioxidant, silane coupling agent, flow agent, stablizer, sanitas etc. can be illustrated.Such additive can use existing known additive by ordinary method.
Next, the structure of the acrylic adhesive tape (or acrylic adhesive sheet) with the binder layer comprising the acrylic pressure-sensitive adhesive compositions with above-mentioned composition is described.
The acrylic adhesive tape of present embodiment, has the binder layer containing acrylic pressure-sensitive adhesive compositions.Acrylic adhesive tape can for regularly, namely unintentionally binder layer is provided with described binder layer, so-called band base material self adhesive tape discretely from this base material in the one or two sides of flat substrates (supporter), or can have the form of the base material of removing support binder layer on the base material of separability, when pasting, so-called without base material self adhesive tape for this binder layer being arranged on release liner (interleaving paper, surface implement the resin sheet etc. of lift-off processing) etc.In the concept of this said self adhesive tape, also can comprise the concept being called adhesive sheet, adhesive label, adhesive film etc.In addition, binder layer can be formed continuously, but also can be the binder layer being formed as the rule such as point-like, strip or being formed as random pattern.
As described base material, can according to the suitable choice for use of the purposes of self adhesive tape such as:
Plastics film, as polypropylene film, ethylene-propylene copolymer film, polyester film, polyvinyl chloride film etc.;
Foam substrate, as polyurethane foam, polyethylene etc.;
Paper, as kraft paper, goffered paper, Japan paper etc.;
Cloth, as cotton, staple fibre cloth etc.;
Non-woven fabrics, as polyester non-woven fabric, nylon nonwoven fabrics etc.;
Tinsel, as aluminium foil, Copper Foil etc.; Deng.
As described plastics film, any one of the film of non-stretched film and stretching (uniaxial extension or biaxial stretch-formed) can be used.In addition, arrange in base material on the face of binder layer, the surface treatments such as silane coupling agent coating, Corona discharge Treatment can be implemented.The thickness of base material suitably can be selected according to object, is generally about 10 μm ~ about 500 μm (typically being about 10 μm ~ about 200 μm).
Binder layer can be the cured layer of acrylic pressure-sensitive adhesive compositions.That is, this binder layer can by acrylic pressure-sensitive adhesive compositions is applied (such as, be coated with) to suitable base material after suitably implement solidification treatment and formed.When carrying out two or more solidification treatment (dry, crosslinked, polymerization etc.), these solidification treatment can simultaneously or the multistage carry out.Use the binder composition of partial polymer (acrylic polymers slurry), typically carry out final copolyreaction (partial polymer is supplied further copolyreaction and forms complete polymkeric substance) as described solidification treatment.Such as, if the binder composition of light solidified, then rayed is implemented.Solidification treatment such as being cross-linked, dry can be implemented as required.Such as, Photocurable adhesive composition has drying if desired, can carry out photocuring after the drying.Use the binder composition of all-polymer, typically implement drying (heat drying) as required, be cross-linked etc. processes as described solidification treatment.
The coating of acrylic pressure-sensitive adhesive compositions, can use such as gravure roll coating machine, reverse roll coater, roller to lick the usual coating machine such as formula coating machine, dipping roll coater, metering bar coater, knife coater, spraying machine and carry out.In addition, when band base material self adhesive tape, binder composition can be applied directly on base material and form binder layer, also the binder layer formed on release liner can be transferred on base material.
The thickness of binder layer is not particularly limited, and is usually set as such as being more than about 10 μm, preferably more than about 20 μm, more preferably from about more than 30 μm, can realize good tackiness thus.Such as, it is suitable for the thickness of binder layer being set as about 10 ~ about 250 μm.
The acrylic adhesive tape of present embodiment, such as, can be suitable for comprising PP(polypropylene), ABS(acrylonitrile-butadiene-styrene copolymer), SBS(styrene-butadiene-styrene block copolymer), PC(polycarbonate), PVC(polyvinyl chloride), PMMA(plexiglass) etc. the metal component of the various resins, SUS, aluminium etc. of acrylic resin engage (fixing) purposes to the surface of automobile (its car body film), residential building material, family's electrical article etc.
In addition, the acrylic adhesive tape of present embodiment, can be suitable for the purposes pasted by various optical component on such as liquid crystal cells or optical polyester film, contact panel component etc.Therefore, in the technology that this shows, duplexer optical component being provided with the binder layer comprising acrylic pressure-sensitive adhesive compositions is included in.This duplexer typically has the mode utilizing release liner to protect the binder layer on optical component.The optical component being provided with binder layer like this, such as, can easily paste on the surface etc. of plastic covering lens panel, glass, liquid crystal cells.Optical component is not particularly limited, and can be polarizing film, phase-contrast film, transparent conductive film (ito thin film) etc.Such optical component, can for comprising the single layer structure of same material, also can for comprising the multilayered structure of multiple material.Optical component is formed the method for binder layer, suitably can adopt direct applying mode or printing transferring method in the same manner as form the situation of binder layer on base material.Typically the binder layer formed on release liner is transferred on the fundamental plane of optical component.
As mentioned above, the acrylic pressure-sensitive adhesive compositions of present embodiment, containing acrylic polymers (A), described acrylic polymers (A) containing having the vinyl monomer of nitrogen-atoms as monomeric unit in skeleton, and does not contain carboxyl group-containing monomer in fact; (methyl) acrylic polymers (B), the weight-average molecular weight of described (methyl) acrylic polymers (B) is more than 1000 and lower than 30000.Therefore, when using this acrylic pressure-sensitive adhesive compositions to form binder layer, the tackiness of acrylic adhesive tape can be improved.
Embodiment
Below, explain the present invention based on embodiment, but in any case the present invention is not limited to these embodiments.
The composition of the acrylic pressure-sensitive adhesive compositions of embodiment 1 ~ 9, comparative example 1 ~ 6 is as shown in table 2.
Table 2
The compound that shortenings in table 2 is expressed as follows.
2EHA: ethyl acrylate
NVP:N-vinyl-2-pyrrolidone
AA: vinylformic acid
DCPMA: methacrylic acid tetrahydrochysene dicyclopentadiene base ester
IBXMA: isobornyl methacrylate
DCPA: vinylformic acid tetrahydrochysene dicyclopentadiene base ester
CHMA: cyclohexyl methacrylate
IBXA: isobornyl acrylate
ADMA: methacrylic acid-1-adamantane esters
ADA: vinylformic acid-1-adamantane esters
MMA: methyl methacrylate
DCPMA is low: the polymerization degree is lower than DCPMA(embodiment 1,2) methacrylic acid tetrahydrochysene dicyclopentadiene base ester
GSH acid: Thiovanic acid
GSH:2-mercaptoethanol
LSH: lauryl mercaptan
The preparation of ((methyl) acrylic polymers 1(DCPMA as (B) composition))
100 parts by weight of toluene, 100 weight parts of methacrylic acid tetrahydrochysene dicyclopentadienes base ester (DCPMA) (trade(brand)name: FA-513M, Hitachi Chemical Co., Ltd. manufactures) and the 3 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 1 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 1 is 175 DEG C, and weight-average molecular weight is 4600.
The preparation of ((methyl) acrylic polymers 2(DCPMA as (B) composition))
By 100 parts by weight of toluene, 100 weight parts of methacrylic acid tetrahydrochysene dicyclopentadiene base ester (DCPMA) (trade(brand)names: FA-513M, Hitachi Chemical Co., Ltd. manufacture) and 3 weight parts put in four-hole boiling flask as the 2 mercapto ethanol (THIOGLYCOL, GSH) of chain-transfer agent.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 2 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 2 is 175 DEG C, and weight-average molecular weight is 3600.
The preparation of (low as (methyl) acrylic polymers 3(DCPMA of (B) composition))
100 parts by weight of toluene, 60 weight parts of methacrylic acid tetrahydrochysene dicyclopentadienes base ester (DCPMA) (trade(brand)name: FA-513M, Hitachi Chemical Co., Ltd. manufactures) and the 5 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 75 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 75 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 3 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 3 is 175 DEG C, and weight-average molecular weight is 3000.
The preparation of ((methyl) acrylic polymers 4(DCPMA/IBXMA40 as (E) composition))
100 parts by weight of toluene, 60 weight parts of methacrylic acid tetrahydrochysene dicyclopentadienes base ester (DCPMA) (trade(brand)name: FA-513M, Hitachi Chemical Co., Ltd. manufactures), 40 weight parts of methacrylic acid isobornyl thiocyanoacetates (IBXMA) and the 3 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 4 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 4 is 174 DEG C, and weight-average molecular weight is 4800.
The preparation of ((methyl) acrylic polymers 5(DCPA as (B) composition))
100 parts by weight of toluene, 100 parts by weight of acrylic acid tetrahydrochysene dicyclopentadienes base ester (DCPA) (trade(brand)name: FA-513AS, Hitachi Chemical Co., Ltd. manufactures) and 8 weight parts are put in four-hole boiling flask as the lauryl mercaptan (LSH) of chain-transfer agent.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 5 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 5 is 120 DEG C, and weight-average molecular weight is 3600.
The preparation of ((methyl) acrylic polymers 6(CHMA as (B) composition))
100 parts by weight of toluene, 100 weight parts of methacrylic acid cyclohexyls (CHMA) and the 3 weight parts 2 mercapto ethanol (THIOGLYCOL, GSH) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 6 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 6 is 66 DEG C, and weight-average molecular weight is 3700.
The preparation of ((methyl) acrylic polymers 7(IBXMA as (B) composition))
100 parts by weight of toluene, 100 weight parts of methacrylic acid isobornyl thiocyanoacetates (IBXMA) and the 3 weight parts 2 mercapto ethanol (THIOGLYCOL, GSH) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 7 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 7 is 173 DEG C, and weight-average molecular weight is 3100.
The preparation of ((methyl) acrylic polymers 8(IBXA as (B) composition))
100 parts by weight of toluene, 100 parts by weight of acrylic acid isobornyl thiocyanoacetates (IBXA) and the 3 weight parts 2 mercapto ethanol (THIOGLYCOL, GSH) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 8 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 8 is 97 DEG C, and weight-average molecular weight is 3300.
The preparation of ((methyl) acrylic polymers 9(ADMA as (B) composition))
100 parts by weight of toluene, 100 weight parts of methacrylic acid-1-adamantane esters (ADMA) and the 3 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 9 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 9 is 250 DEG C, and weight-average molecular weight is 4100.
The preparation of ((methyl) acrylic polymers 10(ADA as (B) composition))
100 parts by weight of toluene, 100 parts by weight of acrylic acid-1-adamantane esters (ADA) and the 3 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 10 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 10 is 153 DEG C, and weight-average molecular weight is 3500.
The preparation of ((methyl) acrylic polymers 11(ADA/MMA40 as (B) composition))
100 parts by weight of toluene, 60 parts by weight of acrylic acid-1-adamantane esters (ADA), 40 parts by weight of methylmethacrylate (MMA) and the 3 weight parts Thiovanic acid (GSH acid) as chain-transfer agent is put in four-hole boiling flask.Then, stir after 1 hour in nitrogen atmosphere at 70 DEG C, drop into the Diisopropyl azodicarboxylate of 0.2 weight part as thermal polymerization, 70 DEG C of reactions 2 hours, then 80 DEG C of reactions 2 hours.Then, under reaction solution being put into the temperature atmosphere of 130 DEG C, dry removing toluene, chain-transfer agent and unreacted monomer, obtain (methyl) acrylic polymers 11 of solid state.The second-order transition temperature of gained (methyl) acrylic polymers 11 is 132 DEG C, and weight-average molecular weight is 4100.
The preparation of (the acrylic polymers slurry 1(2EHA/NVP=86/14 as (A) composition))
86 parts by weight of acrylic acid-2-ethylhexyls (2EHA), 14 weight part NVPs (NVP), 0.05 weight part Photoepolymerizationinitiater initiater (trade(brand)name " イ Le ガ キ ユ ア 184 ", Ciba Specialty Chemicals manufacture) and 0.05 weight part Photoepolymerizationinitiater initiater (trade(brand)name " イ Le ガ キ ユ ア 651 ", Ciba Specialty Chemicals manufacture) are put in four-hole boiling flask.Then, mixture is exposed in ultraviolet partly carries out photopolymerization in a nitrogen atmosphere, obtain the partial polymer (acrylic acid or the like compound slurry 1) of percent polymerization about 11 % by weight thus.
The preparation of (the acrylic polymers slurry 2(2EHA/AA=94/6 as (A) composition))
94 parts by weight of acrylic acid-2-ethylhexyls (2EHA), 6 parts by weight of acrylic acid (AA), 0.05 weight part Photoepolymerizationinitiater initiater (trade(brand)name " イ Le ガ キ ユ ア 184 ", Ciba Specialty Chemicals manufacture) and 0.05 weight part Photoepolymerizationinitiater initiater (trade(brand)name " イ Le ガ キ ユ ア 651 ", Ciba Specialty Chemicals manufacture) are put in four-hole boiling flask.Then, mixture is exposed in ultraviolet partly carries out photopolymerization in a nitrogen atmosphere, obtain the partial polymer (acrylic acid or the like compound slurry 2) of percent polymerization about 8 % by weight thus.
(embodiment 1)
(preparation of acrylic pressure-sensitive adhesive compositions)
In 100 weight part aforesaid propylene acids polymers slurries 1, add (methyl) acrylic polymers 1 and 0.085 weight part Viscoat 295 that 20 weight parts are above-mentioned, then by they Homogeneous phase mixing, prepared acrylic pressure-sensitive adhesive compositions.
(making of tackiness agent synusia)
Polyester film (the trade(brand)name: MRF of the thickness after one side polysiloxane carries out lift-off processing 38 μm, polyester Co., Ltd. of Mitsubishi Chemical manufacture) lift-off processing face on, the mode being 50 μm with final thickness is coated with above-mentioned acrylic pressure-sensitive adhesive compositions and forms coating.Then, the polyester film (trade(brand)name: MRN, polyester Co., Ltd. of Mitsubishi Chemical manufactures) of the thickness 38 μm after the surface coverage one side polysiloxane of the acrylic pressure-sensitive adhesive compositions of coating carries out lift-off processing makes the lift-off processing face of this film be coated side.Thus, by coating (binder layer) starvation of acrylic pressure-sensitive adhesive compositions.On the tackiness agent synusia obtained like this, black lamp (Toshiba Corporation's system) is used to irradiate 360 seconds illumination 5mW/cm 2the ultraviolet of (being used in the ト プ コ Application UVR-T1 that about 350nm has a peak response to measure).The gel fraction of the binder layer that the acrylic pressure-sensitive adhesive compositions obtained like this is formed is 61.5 % by weight.The polyester film that the two sides of binder layer covers paves use as peeling liner.
(embodiment 2)
Above-mentioned (methyl) acrylic polymers 2, the 0.085 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 67.7%.
(embodiment 3)
Above-mentioned (methyl) acrylic polymers 4, the 0.14 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 68.5%.
(embodiment 4)
Above-mentioned (methyl) acrylic polymers 6,0.14 weight part 1 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, 6-hexanediyl ester, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 74.9%.
(embodiment 5)
Above-mentioned (methyl) acrylic polymers 7, the 0.1 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 68.4%.
(embodiment 6)
Above-mentioned (methyl) acrylic polymers 8, the 0.1 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 71.9%.
(embodiment 7)
Above-mentioned (methyl) acrylic polymers 9, the 0.12 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 74.7%.
(embodiment 8)
Above-mentioned (methyl) acrylic polymers 10, the 0.1 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 74.6%.
(embodiment 9)
Above-mentioned (methyl) acrylic polymers 11, the 0.12 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 64.9%.
(comparative example 1)
In the acrylic polymers slurry 1 that 100 weight parts are above-mentioned, add 0.045 weight part 1,6 hexanediol diacrylate, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 77.4%.
(comparative example 2)
In the acrylic polymers slurry 2 that 100 weight parts are above-mentioned, add 0.07 weight part 1,6 hexanediol diacrylate, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 75.2%.
(comparative example 3)
Above-mentioned (methyl) acrylic polymers 6,0.11 weight part 1 of 20 weight parts is added in the acrylic polymers slurry 2 that 100 weight parts are above-mentioned, 6-hexanediyl ester, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 67.7%.
(comparative example 4)
Above-mentioned (methyl) acrylic polymers 3, the 0.18 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 2 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 62.1%.
(comparative example 5)
Above-mentioned (methyl) acrylic polymers 5,0.11 weight part 1 of 20 weight parts is added in the acrylic polymers slurry 2 that 100 weight parts are above-mentioned, 6-hexanediyl ester, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 69.7%.
(comparative example 6)
Above-mentioned (methyl) acrylic polymers 7, the 0.14 weight part Viscoat 295 of 20 weight parts is added in the acrylic polymers slurry 2 that 100 weight parts are above-mentioned, in addition, operate similarly to Example 1, obtain acrylic pressure-sensitive adhesive compositions and tackiness agent synusia.The gel fraction of the binder layer obtained is 68.7%.
(test method)
[180 ° of peel adhesion tests]
A release liner (polyester film) of the tackiness agent synusia of each embodiment and each comparative example is peeled off, pastes the pet film of thickness 50 μm, gained object is cut into 25mm width as test film.In addition, the polypropylene board (manufacture of model 1600, タ キ ロ Application Co., Ltd.) of the thickness 2mm after preparation Virahol cleans and acrylic acid resin plate (ア Network リ ラ イ ト, Mitsubishi Rayon Co. Ltd. manufactures).Then, another release liner (polyester film) of tackiness agent synusia is peeled off, the adhesive face of tackiness agent synusia is pasted on polypropylene board and acrylic acid resin plate by 2kg roller back and forth movement.
Tackiness agent synusia is pasted after on polypropylene board and acrylic acid resin plate, under the environment of 23 DEG C, place 30 minutes (initial stage).In addition, tackiness agent synusia is pasted after on polypropylene board and acrylic acid resin plate, under the environment of 40 DEG C, after 48 hours, under the environment of 23 DEG C, place 30 minutes (normality).For each tackiness agent synusia of initial stage condition and normality condition, the other end of adhesive sheet oxidant layer is peeled off with the direction of delaminate of the speed of 300mm/ minute along 180 degree, measures the bounding force to adherend (resistibility) (unit: N/25mm) now.Polypropylene board and the acrylic acid resin plate bounding force separately in the early stage under condition and normality condition is evaluated as good (zero), lower than being evaluated as during 16N/25mm bad (×) when being more than 16N/25mm.Measurement result is as shown in table 3.
[resistance to resiliency test]
The tackiness agent synusia of each embodiment and comparative example is cut into wide 10mm, long 90mm and the object obtained paste thickness 0.5mm, width 10mm, length 90mm cleaning aluminium sheet on, it can be used as test film.Then, by mode pliability test sheet that the aluminium sheet side of test film is 50mm along cylinder with curvature R.Then, another release liner (polyester film) of tackiness agent synusia is peeled off, and is laminated on above-mentioned polypropylene board.Test film is being laminated under the state on polypropylene board, at normal temperature (25 DEG C) after 7 hours, is measuring the distance that tackiness agent synusia tilts, distance (center line averages at two ends) (unit: mm) namely from the surface of polypropylene board to binder layer.The distance tilted is evaluated as good (zero) when being below 10mm, and the distance of tilting is more than being evaluated as during 10mm bad (×).Measurement result is as shown in table 3.In addition, the numerical value shown in table 3 is the mean value for any number of point.
[preserving property test]
A release liner (polyester film) of the tackiness agent synusia of each embodiment and each comparative example is peeled off, pastes the pet film of thickness 50 μm, gained object is cut into 10mm width as test film.On special carte after cleaning with toluene, paste the adhesive face of test film with the area of wide 10mm, long 20mm, and place 30 minutes under the environment of 60 DEG C.Then, hang weight in one end of test film and make the load applying 500g on shear direction, weight is placed 2 hours with vacant state under the environment of 60 DEG C, evaluates preserving property.The average evaluation that test film does not fall is good (zero), and the average evaluation fallen is bad (×).Measurement result is as shown in table 3.
Table 3
As shown in table 3, the bounding force to polypropylene board of comparative example 1,2,5,6 is all bad under normality condition under condition in the early stage.In addition, the bounding force to polypropylene board of comparative example 3 is good under condition in the early stage, but bad under normality condition.In addition, the bounding force to polypropylene board of comparative example 4 is good under normality condition, but bad under condition in the early stage.In addition, the bounding force to acrylic acid resin plate of comparative example 1 is good under normality condition, but bad under condition in the early stage.In addition, the bounding force to acrylic acid resin plate of comparative example 5 is good under condition in the early stage, but bad under normality condition.On the other hand, embodiment 1 ~ 9 is all good to the bounding force in arbitrary situation of polypropylene board and acrylic acid resin plate both sides condition and normality condition in the early stage.That is, confirm any one embodiment compared with comparative example 1 ~ 6, tackiness all improves.In addition, confirm compared with comparative example 1,2,4 ~ 6, the resistance to rebound resilience of any one embodiment all improves.In addition, in whole embodiment and comparative example, observe good preserving property (cohesive force).Therefore, confirm embodiment 1 ~ 9 and have excellent bounding force, excellent resistance to rebound resilience and excellent preserving property concurrently.In addition, although compared with the comparative example 1 not containing acrylic acid or the like oligopolymer identical with each embodiment with acrylic polymers, the bounding force and the resistance to rebound resilience that confirm any one embodiment improve.
Industrial applicability
The present invention can be applied to acrylic pressure-sensitive adhesive compositions and acrylic adhesive tape.

Claims (5)

1. an acrylic pressure-sensitive adhesive compositions, is characterized in that,
Containing acrylic polymers (A), described acrylic polymers (A) containing having the vinyl monomer of nitrogen-atoms as monomeric unit in skeleton, and does not contain carboxyl group-containing monomer in fact; With
(methyl) acrylic polymers (B), the weight-average molecular weight of described (methyl) acrylic polymers (B) is more than 1000 and less than 4800.
2. acrylic pressure-sensitive adhesive compositions as claimed in claim 1, wherein,
Described acrylic polymers (A) is the multipolymer that (methyl) acrylate described vinyl monomer and following general formula (1) represented carries out copolymerization as neccessary composition and obtain,
CH 2＝C(R 1)COOR 2(1)
In formula (1), R 1for hydrogen atom or methyl, R 2for the alkyl of alicyclic hydrocarbon radical or carbonatoms 1 ~ 12.
3. acrylic pressure-sensitive adhesive compositions as claimed in claim 1 or 2, wherein,
Described vinyl monomer is one or more monomers in the group that is selected from the N-vinyl cyclic acid amides that represented by following general formula (2) and (methyl) acrylic amide and forms,
In formula (2), R 3for the organic group of divalence.
4. acrylic pressure-sensitive adhesive compositions as claimed in claim 1 or 2, wherein,
The content of described (methyl) acrylic polymers (B) is 2 ~ 70 weight parts relative to acrylic polymers (A) 100 weight part.
5. an acrylic adhesive tape, is characterized in that,
There is the binder layer containing the acrylic pressure-sensitive adhesive compositions according to any one of Claims 1-4.
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